Pollution characteristics and environmental risk assessment of typical veterinary antibiotics in livestock farms in Southeastern China

Scientific interest in pollution from antibiotics in animal husbandry has increased during recent years. However, there have been few studies on the vertical exposure characteristics of typical veterinary antibiotics in different exposure matrices from different livestock farms. This study explores the distribution and migration of antibiotics from feed to manure, from manure to soil, and from soil to vegetables, by investigating the exposure level of typical antibiotics in feed, manure, soil, vegetables, water, fish, and pork in livestock farms. A screening environmental risk assessment was conducted to identify the hazardous potential of veterinary antibiotics from livestock farms in southeast China. The results show that adding antibiotics to drinking water as well as the excessive use of antibiotic feed additives may become the major source of antibiotics pollution in livestock farms. Physical and chemical properties significantly affect the distribution and migration of various antibiotics from manure to soil and from soil to plant. Simple migration models can predict the accumulation of antibiotics in soil and plants. The environmental risk assessment results show that more attention should be paid to the terrestrial eco-risk of sulfadiazine, sulfamethazine, sulfamethoxazole, tetracycline, oxytetracycline, chlorotetracycline, ciprofloxacin, and enrofloxacin, and to the aquatic eco-risk of chlorotetracycline, ciprofloxacin, and enrofloxacin. This is the first systematic analysis of the vertical pollution characteristics of typical veterinary antibiotics in livestock farms in southeast China. It also identifies the ecological and human health risk of veterinary antibiotics.     

施粪肥土壤中抗生素的提取条件优化及残留特征

为确立高效的土壤抗生素提取条件,揭示施用粪肥土壤中抗生素的残留水平,分别采集江苏省常州市某养猪场新鲜猪粪样品6份、施用粪肥及无机肥水稻土壤样品各13份,对土壤抗生素提取液配比与超声提取时间进行筛选,利用高效液相色谱-串联质谱（HPLC-MS/MS）对生猪粪便和土壤中的四大类（四环素类、磺胺类、喹诺酮类和大环内脂类）15种抗生素含量进行检测分析。结果表明,最优提取条件选择为：提取液配比为甲醇：EDTA=1：1,超声提取时间为10 min,四环素类抗生素的加标回收率为73.2%~93.4%,磺胺类为81.2%~101.1%,喹诺酮类为106.3%~110.8%。该养猪场猪粪与施粪肥土壤中均未检测到大环内脂类抗生素,其余各类抗生素平均残留量从高到低排序分别为：猪粪中四环素类 > 磺胺类 > 喹诺酮类;施粪肥土壤中四环素类 > 喹诺酮类 > 磺胺类,四环素类是最主要的抗生素污染物,残留量分别为猪粪中1.9~12.5 mg·kg-1、施粪肥土壤中23.9~212.4 μg·kg-1;施无机肥土壤中未检测出抗生素,施粪肥土壤中的抗生素来源于生猪粪便。     

Occurrence of veterinary antibiotics in animal wastewater and surface water around farms in Jiangsu Province, China

The objective of this investigation was to obtain a broad profile of veterinary antibiotics residues in animal wastewater and surface water around large-scale livestock and poultry farms in Jiangsu Province of China. Therefore, 53 samples collected from 27 large-scale animal farms in 11 cities and counties of Jiangsu Province in 2009, were monitored for 10 selected veterinary antibiotics using solid phase extraction and high performance liquid chromatography/electrospray ionization-tandem mass spectrometry (HPLC/ESI-MS/MS) techniques. Ten veterinary antibiotics were found in animal wastewaters, eight antibiotics were detected in pond waters, and animal farm-effluents and river water samples were contaminated by nine antibiotics. The most frequently detected antibiotics were sulfamethazine (75%), oxytetracycline (64%), tetracycline (60%), sulfadiazine (55%) and sulfamethoxazole (51%) which were detected with a maximum concentration of 211, 72.9, 10.3, 17.0 and 63.6 μg L⁻¹, respectively. The maximum concentration of 0.55 μg L⁻¹ for cyromazine, 3.67 μg L⁻¹ for chlortetracycline, 0.63 μg L⁻¹ for sulfadoxine, 39.5 μg L⁻¹ for doxycycline and 0.64 μg L⁻¹ for sulfaquinoxaline were determined in the collected samples. In general, the maximum concentration of the selected veterinary antibiotics was detected in animal wastewaters except for chlortetracycline in animal farm-effluents. In addition, residue levels of selected veterinary antibiotics in animal wastewater and surface water around the farms were related to animal species and have a high spatial variation.     

江苏省典型工业源挥发性有机物排污特征与减排潜力分析

VOCs是臭氧和二次有机气溶胶等复合型污染的前驱体。基于原辅料和生产工艺的角度,构建江苏省内人造板、印刷、电子、橡胶和塑料、制药、化工、喷涂为代表的典型工业行业VOCs成分谱。通过最大增量反应活性系数(MIR) 、气溶胶生成系数(FAC),依据原辅料、产品和工艺的区别,分析各行业、企业VOCs 组分区别与臭氧生成潜势和二次颗粒物生成潜势。结果表明：橡胶和塑料行业单位OFP最高,约为4.09 g·g⁻¹;SOA较高的印刷、制药、涂装、橡胶和塑料行业,其值约为1.5 g·g⁻¹;通过MIR 和FAC 系数模型可知,橡胶和塑料行业是O₃污染管控重点,印刷、制药、涂装、橡胶和塑料行业是二次气溶胶的管控重点。基于江苏省典型工业行业VOCs特征,分析我国现行VOCs治理技术指南推荐工艺与现存低效治理工艺的差异,以估算全国典型工业行业VOCs年产污量和污染特性减排潜力,可为VOCs管理相关法规政策制定提供依据。     

化学原料药行业挥发性有机废气污染特征与治理中的主要问题及建议

化学原料药制造行业是挥发性有机废气(VOCs)排放重点监管行业。原料药生产过程中VOCs排放具有排放节点多、成份复杂等特点。在阐述典型原料药生产过程中VOCs产生环节的基础上,分析了制药企业VOCs治理普遍面临的治理技术缺乏针对性、无组织废气收集不足、企业废气自行监测能力不足等难点问题,并对制药企业VOCs治理提出了加强有机废气成分溯源监测和规范废气收集等前瞻性建议,以期为提高该行业的VOCs治理效果并促进制药行业的可持续发展提供参考。     

Determination of antibiotics in sewage from hospitals, nursery and slaughter house, wastewater treatment plant and source water in Chongqing region of Three Gorge Reservoir in China

Sewage samples from 4 hospitals, 1 nursery, 1 slaughter house, 1 wastewater treatment plant and 5 source water samples of Chongqing region of Three Gorge Reservoir were analyzed for macrolide, lincosamide, trimethoprim, fluorouinolone, sulfonamide and tetracycline antibiotics by online solid-phase extraction and liquid chromatography-tandem mass spectrometry. Results showed that the concentration of ofloxacin (OFX) in hospital was the highest among all water environments ranged from 1.660 μg/L to 4.240 μg/L and norfloxacin (NOR, 0.136-1.620 μg/L), ciproflaxacin (CIP, ranged from 0.011 μg/L to 0.136 μg/L), trimethoprim (TMP, 0.061-0.174 μg/L) were commonly detected. Removal range of antibiotics in the wastewater treatment plant was 18-100% and the removal ratio of tylosin, oxytetracycline and tetracycline were 100%. Relatively higher removal efficiencies were observed for tylosin (TYL), oxytetracycline (OXY) and tetracycline (TET)(100%), while lower removal efficiencies were observed for Trimethoprim (TMP, 1%), Epi-iso-chlorotetracycline (EICIC, 18%) and Erythromycin-H₂O (ERY-H₂O, 24%). Antibiotics were removed more efficiently in primary treatment compared with those in secondary treatment.     

典型南方水源溶解性有机物荧光特性变化与去除

于2014年4-9月,研究我国一典型南方水源溶解性有机物(DOM)的荧光特性变化与去除情况,同时分析了DOM荧光组分与三氯乙醛生成势(CHFP)的相关性。结果表明,该水源DOM主要以芳香性蛋白质类物质组成,溶解性微生物代谢产物类物质、富里酸类物质和腐殖酸类物质含量逐渐增加;5个荧光区域的积分体积(ΦⅠ,n、ΦⅡ,n、ΦⅢ,n、ΦⅣ,n和ΦⅤ,n)所占总体积(ΦT,n)平均比例依次为:13.55%、27.53%、25.00%、16.02%和17.91%;原水DOM的CHFP范围为27.06~81.20μg/L,平均值为46.60μg/L,三氯乙醛(CH)前体物含量与水体中溶解性微生物代谢产物类物质相关性最好;与常规处理工艺相比,O3/BAC深度处理工艺对于溶解性微生物代谢产物类物质的去除率大幅提高,更有利于CH的控制。     

Determinations of hexabromocyclododecane (HBCD) isomers in channel catfish, crayfish, hen eggs and fish feeds from China by isotopic dilution LC-MS/MS

HBCD is widely used brominated flame retardant, which is increasingly reported in the environment. A new isotopic dilution LC-MS/MS method was developed to determine three HBCD isomers, α-, β- and γ-HBCD in channel catfish, crayfish, hen eggs and fish feeds in this study, and especially for the first time HBCD isomers composition in crayfish, hen eggs and fish feeds. Soxhlet extractor and GPC cleanup were used, some important steps and crucial parameters were modified and intensified compared with other literatures, and LC and MS/MS conditions were optimized. The limits of quantitation values of 0.01, 0.005 and 0.005 ng g⁻¹ wet weight in channel catfish and crayfish were calculated for three HBCD isomers, respectively; so did 0.1, 0.05 and 0.05 ng g⁻¹ wet weight in eggs and 0.2, 0.1, 0.1 ng g⁻¹ wet weight in fish feeds. Recoveries of α-HBCD, β-HBCD and γ-HBCD were ranged between 75% and 105% for these productions at medium and high-level spiked samples, and between 60% and 85% at low-level spiked samples. The established methods were therefore suitable for the determinations of three HBCD isomers in these productions at trace contamination levels. Moreover, thirty commercial channel catfish, crayfish, hen eggs and fish feeds samples collected from local markets, and thirty home-produced hen eggs from private owners in Hubei province of China, were analyzed to determine whether these productions were contaminated by HBCD. Using the established methods, HBCD emerged in 4 of 30 fish feeds and 3 of 30 home-produced eggs, and in low-ng g⁻¹ wet weight.